JPS6033875B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for improving the stability of a dispersion-based mixture of pulverized coal and oil obtained by a dry grinding process.

Conventionally, although pulverized coal has a low price per calorific value, it has disadvantages such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large space required for storage. There was a problem with fuel.

A mixture of pulverized coal and oil does not have the above-mentioned drawbacks and has high practical value because it has a lower price per calorific value than oil alone.
However, simply mixing pulverized coal and oil does not yield a satisfactory pulverized coal-oil mixture because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity. Therefore, it is an important challenge to find additives that improve stability.
Mr. Greenstreet of England was examined in 20th King, Mr. Leadbeater of England in 1922, Mr. Balke of Germany in 1932, and Mr. Uhde of Germany in 19338.

However, soap, milk, gelatin, starch, albumin,
Rubber, heavy paraffin, cyclic olefin, resinate,
Even when additives such as oleate, stearate, palmitate, creosote oil, alkali, anthracene oil, tar, phenol, pyridine, aniline, naphthalene, etc. - The stability of the oil mixture is poor (less than one month) and the amount of additives is large, making the price of the pulverized coal-oil mixture high;
It was not put into practical use due to problems with stability and economy. An example of this can also be seen in U.S. Patent No. 3,615,095.
There were problems in practical use because of poor stability and the large amount of additives required.

In order to overcome the above-mentioned problems and put into practical use a pulverized coal-oil mixture using a dispersion method, the present inventors have conducted extensive research and found that an effective additive to a pulverized coal-oil mixture obtained by a dry pulverization method has been found. succeeded in finding a drug,
This made practical application possible.

The present invention improves stability by more than three times compared to conventional methods, and even when stored for a long period of time at room temperature or high temperature, sedimentation of fine coal hardly occurs, and even if it occurs slightly, due to the excellent action of this drug, Because there is almost no agglomeration of settled pulverulent coal,
It can be reflowed with only a very simple female frame.

Of course, in the case of a short period of time (about 15 days), there is no need for a stirring frame. This has made it possible to safely transport the pulverized coal-oil mixture by tanker over a long period of time, or to transport it through pipelines and piping. In addition, the amount of this drug used was smaller than that of the conventional method, and from an economical point of view, it was possible to further promote the practical application of powdered coal-oil mixtures. The coal used in the fine coal-oil mixture includes, for example, anthracite coal, hawk blue coal, subclear blue coal,
Any type of coal, such as lignite, can be used, regardless of its type, origin, chemical composition, or moisture content. If such coal is dry-pulverized using an ordinary mill, powdered coal can be produced in large quantities. Further, there is no problem whether the moisture in the coal is removed by drying or not. However, lignite, etc., which have a high moisture content, have a small calorific value per weight, so they are usually dried. Judging from the fuel properties, the particle size of the pulverized coal is usually preferably 200 French or less, and even smaller particle size of 100 French or less is preferred, but as far as the physical properties such as the stability of the pulverized coal-oil mixture are concerned,
Furthermore, there is no problem even if the particle size is large.

The content of this pulverized coal is less than 60% by weight based on the final mixture, and if the f number pulverized coal is contained in an amount of 6% by weight or more, the viscosity becomes extremely high and fluidity is lost, which is not preferable. If the amount is less than 20% by weight, it is also not preferred because there is little advantage in terms of price due to the inclusion of pulverized coal. Therefore, less than 60% by weight can be mixed, but 20 to 50% by weight is more preferred.

In addition, the oil used in the pulverized coal-oil mixture includes coal crude oil, various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil,
Mainly B heavy oil, C heavy oil, etc., as well as ethylene cracked residual oil,
Oils and waste oils commonly used as fuel such as creosote oil, anthracene oil, and various blended oils, such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (mixed oil of machine oil, cutting oil, cleaning oil, etc.) , waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these.

Among these, it is particularly preferable to use petroleum crude oil, B heavy oil, and C heavy oil.

Even if a powdered coal-oil mixture is made using a pre-mixed pond,
After making a pulverized coal-oil mixture using a single oil (preferably petroleum crude oil or heavy oil), it may be mixed with other oils or co-fired.
Water may be mixed into the coal-oil mixture by the moisture contained in the coal, or may be added by the manufacturer, but transportation costs, storage costs, and other general and administrative costs will increase due to the volume of water. ,
Furthermore, it is not preferable because it increases the heat of evaporation and increases heat loss, so the smaller the amount, the better.

On the other hand, water has the property of improving the stability of the pulverized coal-oil mixture and has the effect of reducing the amount of N○k and vizine in the exhaust gas during combustion.

Therefore, it can be used as desired depending on the purpose, but adding more than 5% by weight should be avoided as it inhibits combustion.

The pulverized coal-oil mixture additive produced by the dispersion method using the dry pulverization method according to the present invention has a molecular weight of 1,000 to 100,000, preferably 2.
This additive contains as an essential component a compound obtained by condensing 000 to 20,000 polyether compounds using formalin.

The additive for a mixture of pulverized coal and oil obtained by the dry pulverization method of the present invention can provide a stable pulverized coal-oil mixture by simply adding and mixing a very small amount of 31% by weight or less.

It goes without saying that the effect will not deteriorate even if it is added in an amount of 1% by weight or more, but the effect is significant even if it is added at 0.2% by weight, for example, and there is no need to add more for economic reasons.

In addition, this essential component may be used in combination with anionic, cationic, nonionic, or amphoteric surfactants, but as long as they do not exist in an amount of 5% or more, preferably 20% or more of the total amount of additives. It won't happen.

By the way, finely pulverizing coal using the dry pulverization method
Since it has already been produced in large quantities, it can be said that this is the most preferable pulverization method for producing fuel that is regularly consumed in large quantities. When used in a pulverized coal-oil mixture containing at least less than % by weight of fuel oil, the new fuel can be supplied in large quantities because it exhibits the outstanding effects as described above.

Although the mechanism by which the agents of the present invention can exhibit outstanding effects when added in small amounts is unclear, it is likely that these agents are adsorbed onto the surface of powdered coal particles in the oil, and the repulsion and ion repulsion effects caused by the molecular chains of the agents are more than sufficient. It is believed that this prevents the agglomeration and sedimentation of powdered coal particles.

From this point of view, in order to achieve the above effect with a small amount of addition, it is necessary to introduce a polar group for adsorption of drug molecules to the surface of powdered coal particles, and to physically prevent coal particle aggregation. It is thought that the size and bulk of the resulting molecules are required.

All of the drugs of the present invention have such a molecular structure, and are characterized by the significant stericity and bulk of the molecular structure based on polar groups based on polyether groups and crosslinking of high molecular weight polyethers.

As described above, all of the drugs of the present invention have polar groups, that is, hydrophilic groups, in their molecules, so when added to a powdered coal-oil mixture, they adsorb to the surface of powdered coal particles, which have weak hydrophilicity, and Because the molecules are large and bulky, when the particles come close to each other, the steric hindrance of the molecules can prevent particle aggregation and sedimentation, which is thought to be extremely effective. The drug of the present invention is effective either after adding it to a mixture of oil and powdered coal obtained by a dry crushing method, or by adding powdered coal that has been added to oil in advance. .

A stable pulverized coal-oil mixture containing the drug of the present invention can be obtained by swarming the pulverized coal-oil mixture to uniformly dissolve or disperse the drug.

Although the method is not particularly limited, if heating or heating is added at any point in the manufacturing process, the activity of the particle surface will increase and the adsorption of the drug will improve. - The performance of the oil mixture is further improved.
Strong female worship is usually 2h/sec or more, preferably 10m
It refers to adding a shear with a linear velocity of /sec or more,
The light beam may be of any type such as a propeller, turbine type, screen type, line mixer, homogenizer, colloid mill, etc. This strong wave increases the activity of the powdered coal particle surface and increases the chance of contact between the drug and the particle surface. do.

Further, the heating temperature may be increased to 50 oo or more, preferably 7,000 or more, and may be raised to around 200°C. The heating and heating may be applied at any time, for example, when the coal is crushed, when a chemical is added after the coal is crushed, after the coal has been crushed, during storage, or when transported through a pipe. Although this drug is effective even without adding heat or strong azusa, when these conditions are added, the effect increases about twice as much.

Since the present pulverized coal-oil mixture utilizes the additive of the present invention, it can last for more than 5 months at room temperature and 90% even at 70°C.
It is very stable, with almost no difference in performance between the upper and lower layers for more than a day, and even when burned in a boiler or heating furnace, it can be burned in a manner similar to ordinary liquid fuel.

Furthermore, when water is included in the present mixture, it exhibits good effects such as improving flammability, reducing vizine, and reducing N○x. It is not a problem to use rust preventives, anti-pollution agents, combustion improvers, water, carbon materials other than coal, etc., as necessary. Specific examples of the additive for pulverized coal-oil mixtures of the present invention are shown below.

The additive for pulverized coal-oil mixtures according to the present invention is obtained by condensing a polyether compound with a molecular weight of 1,000 to 10,000, preferably 2,000 to 20,000 using formalin, using an aromatic compound as a starting material. The compound used is

Molecular weight 1,0 using the aromatic compound mentioned here as a starting material
00,000 to 100,000, preferably 2,000 and 2 polytern compounds (hereinafter referred to as polyterns) are ethylene oxide, for example, Ethylene oxide, with a compound having an aromatic group and having one or more active hydrogen groups. , propylene oxide or butylene oxide, and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran are addition-polymerized to give a predetermined molecular weight.

In this case, if there are two or more types of alkylene oxide,
Even if the copolymerization type is random, there is no problem even if it is a flock copolymerization. However, if the surfactant is a copolymer type, it is generally a block copolymer type, and preferably, ethylene oxide is added to make the terminal a hydrophilic group. As the compound having an aromatic group and an active hydrogen, the following compounds can be arbitrarily used.

．． Alkylene oxide adducts of alkyl-substituted phenols such as catechol, resorcinol, hydroquinone, pyrogallol, nonylphenol, octylphenol, and dodecylphenols; alkylene oxide adducts of condensed phenols such as bisphenol A and bisphenol S;
Alkylene oxide adducts of naphthols such as diquinaphthalene such as naphresorcinol and Q-naphthohydroquinone.In general, as represented by phenol resins and xylene resins, when reacting polymarin under acidic conditions, aromatic boundaries can be formed. It is known that it has a methylene bridge.

Therefore, in order to condense a polyether compound also using formalin as in the present invention, the above-mentioned known techniques can be used, but it is generally carried out as follows.

That is, 0.1 to 10 equivalents of formalin, preferably 0.5 to 5 equivalents, and 0.05 to 0.005 equivalents of acidic catalyst are added to 1 equivalent of polyether compound to give 60 to 100 equivalents of formalin.
Raise the temperature to 100°C, perform Toazusa for 1 to 3 hours, and then heat to 100°C.
The reaction is completed by raising the temperature to 18,030 ℃.

The powdered charcoal-oil mixture shown in the example table was made into a mold with a diameter of 5 skins and a height of 1
After filling a cylinder of 8 skins and leaving it for one month at a point of 70 oo, the physical properties were measured and the effects of the additive of the present invention were evaluated.

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Claims (1)

[Claims] 1. An aromatic compound used to improve the stability of a dispersion method pulverized coal-oil mixture containing at least less than 60% by weight of pulverized coal obtained by a dry pulverization method and fuel oil. Starting material molecular weight 1,00
An additive for pulverized coal-oil mixtures using a dispersion method, characterized by containing a compound obtained by condensing 0 to 100,000 to 100,000 polyether compounds using formalin.